K. Hattori et al. / Tetrahedron 57 +2001) 4817±4824
4823
0
3
ꢀ
3
7
ꢀ
.5.6. O-Acetyl-4,4 -dimmethoxybenzoin ꢀO-acetylanisoin)
6.82 ꢀd, J8.8 Hz, 2H), 6.86 ꢀd, J8.8 Hz, 2H), 7.07 and
1
13
7.25 ꢀeach d, J8.8 Hz, 2H£2); C NMR ꢀ100 MHz, rt,
6p). Mp 968C; H NMR ꢀ400 MHz, rt, CDCl ): d2.19,
3
.77, 3.82 ꢀeach s, 3H£3), 6.80 ꢀs, 1H), 6.85±6.89 ꢀm, 4H),
CDCl ): d45.1, 55.2, 55.2, 75.0, 113.7, 113.9, 127.1,
3
1
3
.38 ꢀd, J9.0 Hz, 2H), 7.91 ꢀd, J9.0 Hz, 2H); C NMR
130.1, 130.4, 136.0, 158.3, 159.0; MS ꢀEI or FAB) m/z
1
1
100 MHz, rt, CDCl ): d20.8, 55.3, 55.4, 77.1, 113.9,
ꢀ%) no [M ] ꢀ[M 11]) peak; anal. calcd for C H O : C
16 18 3
3
1
1
14.6, 126.1, 127.5, 130.2, 131.1, 160.3, 163.7, 170.5,
92.1; MS ꢀEI) m/z ꢀ%) 314 ꢀ5) [M ]; anal. calcd for
74.40, H 7.02; found: C 74.45, H 7.09.
1
C H O : C 68.78, H 5.77; found: C 68.77, H 5.84.
5
3.5.13. 1,2-Di-2-pyridylethanol ꢀ5q). The product 5q was
afforded in 99% yield from 6q as a light brown oil. H NMR
1
8
18
1
1
.5.7. O-Acetyl-a-pyridoin ꢀ6q). Mp 1228C; H NMR
3
ꢀ400 MHz, rt, CDCl
3
): d3.14 ꢀdd, J9.1 and 16.0 Hz,
ꢀ
400 MHz, rt, CDCl ): d2.24 ꢀs, 3H), 7.18±7.21 ꢀm,
1H), 3.36 ꢀdd, J3.2 and 16.0 Hz, 1H), 5.22 ꢀdd, J3.2
and 9.1 Hz, 1H), 7.14±7.17 ꢀm, 3H), 7.50 ꢀd, J7.8 Hz,
1H), 7.59 ꢀdt, J2.0 and 7.8 Hz, 1H), 7.66 ꢀdt, J1.5 and
3
1
1
7
1
H), 7.38±7.41 ꢀm, 1H), 7.57 ꢀs, 1H), 7.62 ꢀd, J7.8 Hz,
H), 7.71 ꢀdt, J2.0 and 7.8 Hz, 1H), 7.80 ꢀdt, J1.5 and
.8 Hz, 1H), 8.09 ꢀd, J7.8 Hz, 1H), 8.52 ꢀd, J3.9 Hz,
1
3
7.8 Hz, 1H), 8.49±8.53 ꢀm, 2H); C NMR ꢀ100 MHz, rt,
1
3
H), 8.58 ꢀd, J3.9 Hz, 1H); C NMR ꢀ100 MHz, rt,
CDCl ): d44.4, 73.5, 120.3, 121.6, 122.0, 124.0, 136.6,
3
CDCl ): d20.6, 78.0, 122.7, 123.2, 124.4, 127.2, 136.8,
136.7, 148.3, 148.4, 159.3, 162.4; HRMS ꢀEI) calcd for
3
1
1
36.8, 148.8, 149.5, 151.6, 154.5, 170.2, 193.4; MS ꢀEI) m/z
C H N O [M ] 200.0950, found 200.0946.
12 12 2
1
ꢀ
%) 256 ꢀ1) [M ]; anal. calcd for C H N O : C 65.62, H
14 12 2 3
4
.72, N 10.93; found: C 65.62, H 4.72, N 10.89.
3.5.14. 1,3-Diphenylpropanol ꢀ5r). The product 5r agreed
with the analytical data of 2e.
1
.5.8. 3-Acetoxy-3-phenylpropiophenone ꢀ6r). H NMR
3
3.5.15. 1-Phenyl-4,4-dimethyl-3-pentanone ꢀ5s). The
product 5s was afforded in 99% yield from 6s as a pale
ꢀ
400 MHz, rt, CDCl ): d2.02 ꢀs, 3H), 3.32 ꢀdd, J4.9
3
and 16.7 Hz, 1H), 3.71 ꢀdd, J8.3 and 16.7 Hz, 1H), 6.40
1
yellow oil. H NMR ꢀ400 MHz, rt, CDCl ): d1.11 ꢀs,
ꢀ
dd, J4.9 and 8.3 Hz, 1H), 7.25±7.58 ꢀm, 8H), 7.93 ꢀd, J
3
1
H), 2.78±2.88 ꢀm, 4H), 7.19±7.29 ꢀm, 5H); C NMR
3
1
3
9
7
7
1
2
.3 Hz, 2H); C NMR ꢀ100 MHz, rt, CDCl ): d21.0, 45.1,
3
ꢀ
1
[
100 MHz, rt, CDCl ): d26.3, 30.1, 38.5, 44.1, 126.0,
1
M ] 190.1358, found 190.1355.
1.9, 126.5, 128.1, 128.2, 128.6, 128.6, 133.3, 136.7, 140.0,
69.8, 196.1; HRMS ꢀEI) calcd for C H O [M ]
68.1092, found 268.1099.
3
1
28.4, 128.4, 141.6, 214.9; HRMS ꢀEI) calcd for C H O
13 18
1
7
16
3
3
.5.9. 1-Acetoxy-4,4-dimethyl-1-phenyl-3-pentanone ꢀ6s).
1
H NMR ꢀ400 MHz, rt, CDCl ): d1.09 ꢀs, 9H), 2.02 ꢀs,
References
3
3
1
H), 2.82 ꢀdd, J4.9 and 16.9 Hz, 1H), 3.20 ꢀdd, J8.3 and
6.9 Hz, 1H), 6.21 ꢀdd, J4.9 and 8.3 Hz, 1H), 7.26±7.35
1. ꢀa) Rylander, P. N. Hydrogenation Methods, Academic:
New York, 1985. ꢀb) Hudlicky, M. Reductions in Organic
Chemistry, 2nd ed.; ACS: Washington, DC, 1996.
1
3
ꢀ
m, 5H); C NMR ꢀ100 MHz, rt, CDCl ): d21.0, 25.9,
3
4
HRMS ꢀEI) calcd for C H O [M ] 248.1412, found
3.2, 44.2, 72.1, 126.5, 128.1, 128.5, 140.2, 169.7, 211.6;
1
1
5
20
3
2. Selected review: Larock, R. C. In Comprehensive Organic
Transformations, VCH: New York, 1989; pp 527±552.
2
48.1414.
3
. For non-asymmetric hydrogenation, Burk, M. J.; Harper,
T. G. P.; Lee, J. R.; Kalberg, C. Tetrahedron Lett. 1994, 35,
4963±4966 and references cited therein.
3.5.10. 1,2-Diphenylethanol ꢀ5n). The product 5n was
afforded in 98% yield from 6n as a white crystal. Mp
1
6
2
58C; H NMR ꢀ400 MHz, rt, CDCl ): d1.93 ꢀd, J
4. For asymmetric hydrogenation using homogeneous catalysts,
ꢀa) Noyori, R.; Takaya, H. Acc. Chem. Res. 1990, 23, 345±
350. ꢀb) Takaya, H.; Ohta, T. J. Synth. Org. Chem., Jpn. 1993,
51, 1013±1023. ꢀc) Doucet, H.; Ohkuma, T.; Murata, K.;
Yokozawa, T.; Katayama, E.; England, A. F.; Ikariya, T.;
Noyori, R. Angew. Chem., Int. Ed. Engl. 1998, 37, 1703±
1707 and references cited therein.
3
.4 Hz, 1H), 2.99 ꢀdd, J8.3 and 13.4 Hz, 1H), 3.05 ꢀdd,
J4.9 and 13.4 Hz, 1H), 4.88±4.93 ꢀm, 1H), 7.19±7.38 ꢀm,
1
3
1
1
0H); C NMR ꢀ100 MHz, rt, CDCl ): d46.1, 75.3,
3
25.9, 126.6, 127.6, 128.4, 128.5, 129.5, 138.0, 143.8; MS
1
ꢀEI) m/z ꢀ%) 198 ꢀ3) [M ]; anal. calcd for C H O: C 84.81,
1
H 7.12; found: C 84.62, H 7.22.
4
14
5
. For asymmetric transfer hydrogenations using homogeneous
catalysts, ꢀa) Zassinovich, G.; Mestroni, G.; Gladiali, S. Chem.
Rev. 1992, 92, 1051±1069. ꢀb) Noyori, R.; Hashiguchi, S. Acc.
Chem. Res. 1997, 30, 97±102. ꢀc) Petra, D. G. I.; Reek, J. N. H.;
Handgraaf, J.-W.; Meijer, E. J.; Dierkes, P.; Kamer, P. C. J.;
Brussee, J.; Schoemaker, H. E.; van Leeuwen, P. W. N. M.
Chem. Eur. J. 2000, 6, 2818±2829. ꢀd) Petra, D. G. I.; Kamer,
P. C. J.; Spek, A. L.; Schoemaker, H. E.; van Leeuwen,
P. W. N. M. J. Org. Chem. 2000, 65, 3010±3017. ꢀe) Alonso,
D. A.; Nordin, S. J. M.; Roth, P.; Tarnai, T.; Andersson, P. G.
J. Org. Chem. 2000, 65, 3116±3122 and references cited
therein.
3
5
.5.11. 1,2-Di-4-methylphenylethanol ꢀ5o). The product
o was afforded in 100% yield from 6o as a white crystal.
1
Mp 678C; H NMR ꢀ400 MHz, rt, CDCl ): d2.32 and 2.35
3
ꢀ
each s, 3H£2), 2.92 ꢀdd, J8.6 and 13.7 Hz, 1H), 2.99 ꢀdd,
J4.6 and 13.7 Hz, 1H), 4.82 ꢀdd, J4.6 and 8.6 Hz, 1H),
7
2
4
1
.08±7.10 ꢀm, 4H), 7.15 and 7.25 ꢀeach d, J7.8 Hz,
1
3
H£2); C NMR ꢀ100 MHz, rt, CDCl ): d21.0, 21.1,
3
5.6, 75.2, 125.8, 129.1, 129.2, 129.3, 135.0, 136.1, 137.2,
40.9; MS ꢀEI) m/z ꢀ%) 226 ꢀ1) [M ]; anal. calcd for
1
C H O: C 84.91, H 8.02; found: C 84.79, H 8.18.
1
6
18
3
5
1
2
.5.12. 1,2-Di-4-methoxyphenylethanol ꢀ5p). The product
p was afforded in 98% yield from 6p as a white crystal. Mp
6. For asymmetric hydrogenation using heterogeneous catalysts,
Jannes, G.; Dubois, V. Chiral Reactions in Heterogeneous
Catalysis, Plenum: New York, 1995 and references cited
therein.
1
138C; H NMR ꢀ400 MHz, rt, CDCl ): d2.92±2.94 ꢀm,
3
H), 3.77 and 3.79 ꢀeach s, 3H£2), 4.79 ꢀt, J6.6 Hz, 1H),